EP0552252B1 - Gesättigte, lineare polyfluorkohlenwasserstoffe, verfahren zu ihrer herstellung und ihre verwendung in reinigungsmitteln - Google Patents

Gesättigte, lineare polyfluorkohlenwasserstoffe, verfahren zu ihrer herstellung und ihre verwendung in reinigungsmitteln Download PDF

Info

Publication number
EP0552252B1
EP0552252B1 EP91918761A EP91918761A EP0552252B1 EP 0552252 B1 EP0552252 B1 EP 0552252B1 EP 91918761 A EP91918761 A EP 91918761A EP 91918761 A EP91918761 A EP 91918761A EP 0552252 B1 EP0552252 B1 EP 0552252B1
Authority
EP
European Patent Office
Prior art keywords
cfcf
chfchfcf
starting material
hydrogen
chfcf
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91918761A
Other languages
English (en)
French (fr)
Other versions
EP0552252A1 (de
EP0552252A4 (en
Inventor
Carl George Krespan
Velliyur Nott Mallikarjuna Rao
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0552252A1 publication Critical patent/EP0552252A1/de
Publication of EP0552252A4 publication Critical patent/EP0552252A4/en
Application granted granted Critical
Publication of EP0552252B1 publication Critical patent/EP0552252B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C07C17/354—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by hydrogenation

Definitions

  • This invention relates to fluorine-substituted hydrocarbon compounds, their production, and their use for cleaning solid surfaces, and more particularly to polyfluoropentanes, polyfluorohexanes, and polyfluoroheptanes, their production by the reduction of polyfluoroolefin starting materials, and their use as solvents.
  • Boiling point, flammability and solvent power can often be adjusted by preparing mixtures of solvents.
  • solvents e.g., isopropanol and nitromethane
  • 1,1,2-trichloro-1,2,2-trifluoroethane alone e.g., isopropanol and nitromethane
  • solvents e.g., isopropanol and nitromethane
  • Azeotropic compositions exhibit either a maximum or minimum boiling point and do not fractionate upon boiling. These characteristics are also important in the use of the solvent compositions in certain cleaning operations, such as removing solder fluxes and flux residues from printed circuit boards. Preferential evaporation of the more volatile components of the solvent mixtures, which would be the case if the mixtures were not azeotropes, or azeotrope-like, would result in mixtures with changed compositions which may have less desirable properties (e.g., lower solvency for contaminants such as rosin fluxes and/or less inertness toward the substrates such as electrical components).
  • Azeotropic characteristics are also desirable in vapor degreasing operations where redistilled material is isually used for final rinse-cleaning.
  • the vapor defluxing or degreasing system acts as a still.
  • the solvent composition exhibits a constant boiling point (i.e., is an azeotrope or is azeotrope-like) fractionation will occur and undesirable solvent distribution may act to upset the safety and effectiveness of the cleaning operation.
  • azeotropic compositions based upon halohydrocarbons containing fluorine have been discovered and in some cases used as solvents for the removal of solder fluxes and flux residues from printed circuit boards and for miscellaneous vapor degreasing applications.
  • U.S. Patent No. 2,999,815 discloses the azeotrope of 1,1,2-trichloro-1,2,2-trifluoroethane with acetone
  • U.S. Patent No. 3,903,009 discloses a ternary azeotrope of 1,1,2-trichloro-1,2,2-trifluoroethane with nitromethane and ethanol
  • 3,573,213 discloses an azeotrope of 1,1,2-trichloro-1,2,2-trifluoroethane with nitromethane;
  • U.S. Patent No. 3,789,006 discloses the ternary azeotrope of 1,1,2-trichloro-1,2,2-trifluoroethane with nitromethane and isopropanol;
  • U.S. Patent No. 3,728,268 discloses the ternary azeotrope of 1,1,2-trichloro-1,2,2-trifluoroethane with acetone and ethanol;
  • 2,999,817 discloses the binary azeotrope of 1,1,2-trichloro-1,2,2-trifluoroethane and methylene chloride (i.e., dichloromethane); and U.S. Patent No. 4,715,900 discloses ternary compositions of trichlorotrifluoroethane, dichlorodifluoroethane, and ethanol or methanol.
  • solvent compositions which have proven useful for cleaning contain at least one component which is a halogen-substituted hydrocarbon containing chlorine, and there have been concerns raised over the ozone depletion potential of halogen-substituted hydrocarbons which contain chlorine. Efforts are being made to develop compositions which may at least partially replace the chlorine containing components with other components having lower potential for ozone depletion. Azeotropic compositions of this type are of particular interest.
  • U.S. Patent No. 2,550,953 discloses catalytic hydrogenation of unsaturated fluorohydrocarbons.
  • U.S. Patent No. 2,844,636 discloses that 1,1,2,3,4,4-hexafluorobutene can be made by reacting perfluorocyclobutene with hydrogen, using elemental iodine as the catalyst.
  • U. S. Patent No. 4,902,839 discloses certain tetrahydro derivatives of perfluorobutanes, perfluoropentanes and perfluorohexanes, as well as processes for their preparation.
  • novel compounds which contain no chlorine and which may be used alone or in combination with other miscible solvents (e.g., alcohols, ethers, esters, ketones, nitrogen-containing organic compounds such as acetonitrile and nitromethane, and halogenated hydrocarbons) as agents for cleaning solid surfaces.
  • miscible solvents e.g., alcohols, ethers, esters, ketones, nitrogen-containing organic compounds such as acetonitrile and nitromethane, and halogenated hydrocarbons
  • novel compounds of this invention include the group of linear dihydro and trihydro polyfluoropentanes, polyfluorohexanes and polyfluoroheptanes represented by the structural formulae CF 3 CHFCHFCF 2 CF 3 , CF 3 CH 2 CHFCF 2 CF 3 , CF 3 CHFCH 2 CF 2 CF 3 , CF 3 CHFCHFCF 2 CF 2 CF 3 , CF 3 CH 2 CHFCF 2 CF 2 CF 2 , CF 3 CHFCH 2 CF 2 CF 2 CF 3 , CF 3 CF 2 CH 2 CHFCF 2 CF 3 , CF 3 CF 2 CHFCHFCF 2 CF 2 CF 3 , CF 3 CHFCHFCF 2 CF 2 CF 3 , CF 3 CHFCHFCF 2 CF 2 CF 3 , CF 3 CHFCHFCF 2 CF 2 CF 2 CF 3 , CF 3 CHFCHFCF 2 CF 2 CF 2 CF 3 , CF 3 CHFCH 2
  • a process is provided in accordance with this invention for preparing a linear trihydropolyfluoroalkane selected from the group consisting of CF 3 CH 2 CHFCF 2 CF 3 , CF 3 CHFCH 2 CF 2 CF 3 , CF 3 CH 2 CHFCF 2 CF 2 CF 3 , CF 3 CHFCH 2 CF 2 CF 2 CF 3 , CF 3 CF 2 CH 2 CHFCF 2 CF 3 , CF 3 CHFCH 2 CF 2 CF 2 CF 2 CF 3 , CF 3 CH 2 CHFCF 2 CF 2 CF 2 CF 3 , CF 3 CF 2 CHFCH 2 CF 2 CF 2 CF 3 , and CF 3 CF 2 CH 2 CHFCF 2 CF 2 CF 3 , which comprises the step of reacting an olefinic starting material in the liquid phase with hydrogen over a Group VIII metal catalyst (preferably in the presence of a polar solvent); wherein said olefinic starting material has the same number of carbon
  • Another process is provided in accordance with this invention for preparing a linear trihydropolyfluoroalkane selected from the group consisting of CF 3 CH 2 CHFCF 2 CF 3 , CF 3 CHFCH 2 CF 2 CF 3 , CF 3 CH 2 CHFCF 2 CF 2 CF 3 , CF 3 CHFCH 2 CF 2 CF 2 CF 3 , CF 3 CF 2 CH 2 CHFCF 2 CF 3 , CF 3 CHFCH 2 CF 2 CF 2 CF 2 CF 3 , CF 3 CH 2 CHFCF 2 CF 2 CF 2 CF 3 , CF 3 CF 2 CHFCH 2 CF 2 CF 2 CF 3 , and CF 3 CF 2 CH 2 CHFCF 2 CF 2 CF 3 , which comprises the step of reacting an olefinic starting material at an elevated temperature with hydrogen in the presence of at least one material selected from the group consisting of iodine and hydrogen iodide or with hydrogen iodide
  • This invention provides novel saturated linear polyfluorohydrocarbons (i.e., polyfluoroalkanes) which contain two or three hydrogen atoms per molecule.
  • the trihydropolyfluoroalkanes of this invention include the trihydropolyfluoropentanes represented by the structural formulae CF 3 CH 2 CHFCF 2 CF 3 and CF 3 CHFCH 2 CF 2 CF 3 ; the trihydropolyfluorohexanes represented by the structural formulae CF 3 CH 2 CHFCF 2 CF 2 CF 3 , CF 3 CHFCH 2 CF 2 CF 2 CF 3 , and CF 3 CF 2 CH 2 CHFCF 2 CF 3 ; and the trihydropolyfluoroheptanes represented by the structural formulae CF 3 CHFCH 2 CF 2 CF 2 CF 2 CF 3 , CF 3 CH 2 CHFCF 2 CF 2 CF 3 , CF 3 CF 2 CHFCH 2 CF 2 CF 2
  • a process is provided in accordance with this invention for preparing these trihydropolyfluoroalkanes which comprises the step of reacting an olefinic starting material in the liquid phase with hydrogen over a Group VIII metal catalyst, preferably from the palladium group (i.e., Pd, Rh and/or Ru).
  • a Group VIII metal catalyst preferably from the palladium group (i.e., Pd, Rh and/or Ru).
  • Palladium and rhodium are the more preferred metals, with palladium being most preferred.
  • the metal catalyst may be supported, for example on carbon or on alumina.
  • the reduction can be carried out at temperatures in the range of from 0°C to 200°C.
  • the preferred temperature range is from 25°C to 100°C.
  • the pressure of the hydrogenation may be within a wide range, from less than 1 atmosphere to extremely high pressures, but normally pressures from 1 atmosphere to 10 atmospheres is preferred.
  • the molar ratio of hydrogen to olefinic starting material for this process is preferably between about 1:1 and 100:1; and is more preferably between about 2:1 and 10:1.
  • the hydrogen may be provided by continuous or intermittent addition to a reactor containing the olefinic starting material and the catalyst until the desired ratio (based upon the initial amount of starting material) is attained.
  • the hydrogenation is preferably conducted in the presence of a polar solvent.
  • a polar solvent is essential for high selectivity to the trihydro derivatives from the perfluoroolefin starting materials.
  • Suitable polar solvents which may be employed include water, alcohols, glycol, acetic acid, dimethylformamide, N-methyl pyrollidone and triethylamine, or mixtures thereof. Methanol is a preferred polar solvent.
  • polyfluoroolefins having at least 5 carbon atoms may be manufactured by reacting together two selected polyfluoroolefins in the presence of a catalyst of the formula AlX 3 where X is one or more of F, Cl or Br (provided that X is not entirely F).
  • a five carbon perfluoroolefinic starting material may be prepared by the reaction of hexafluoropropene (HFP) with tetrafluoroethylene (TFE).
  • Three carbon perfluoro-olefinic starting materials may be prepared by the reaction, substantially according to the procedure of Example A, of 1,1,1,4,4,4-hexafluoro-2,3-dichloro-2-butene with TFE to yield an intermediate product comprising perfluoro-2,3-dichloro-2-hexene which may then be converted to a mixture of perfluoro-2-hexene and perfluoro-3-hexene by reaction with potassium fluoride in refluxing N-methyl pyrolidone.
  • a mixture of seven carbon perfluoroolefinic starting materials may be prepared by the reaction, substantially according to the procedure of Example A, of hexafluoro-propene with 2 moles of TFE.
  • Another process is provided in accordance with this invention for preparing a linear trihydropolyfluoroalkane selected from the group consisting of CF 3 CH 2 CHFCF 2 CF 3 , CF 3 CHFCH 2 CF 2 CF 3 , CF 3 CH 2 CHFCF 2 CF 2 CF 3 , CF 3 CHFCH 2 CF 2 CF 2 CF 3 , CF 3 CF 2 CH 2 CHFCF 2 CF 3 , CF 3 CHFCH 2 CF 2 CF 2 CF 2 CF 3 , CF 3 CH 2 CHFCF 2 CF 2 CF 2 CF 3 , CF 3 CF 2 CHFCH 2 CF 2 CF 2 CF 3 , and CF 3 CF 2 CH 2 CHFCF 2 CF 2 CF 3 , which comprises the step of reacting an olefinic starting material at an elevated temperature with hydrogen in the presence of at least one material selected from the group consisting of iodine and hydrogen iodide or with hydrogen iodide
  • Hydrogen iodide for the reaction may be provided by several methods.
  • the reaction may be run with stoichiometric HI.
  • the reaction may be run with catalytic amounts of HI in the presence of hydrogen.
  • the reaction may also be run with hydrogen using catalytic amounts of iodine. This latter method is preferred for batch reactions and for ease of handling.
  • This reaction may be accomplished in the absence of supported metal catalysts; and indeed the catalyst for this reaction typically consists essentially of iodine and/or hydrogen iodide.
  • the reaction temperature for this reaction should generally be from 100°C to 500°C.
  • a preferred temperature range is from 200°C to 400°C.
  • This reaction may be run at a pressure of from 3.4 to 340 atm. (50 psi to 5000 psi), with 34 to 102 atm. (500 psi to 1500 psi) being preferred.
  • the amount of hydrogen provided for contact with the olefinic starting material should represent at least one molecule of hydrogen for each olefinic bond to be saturated, and is preferably 10 times said minimum, or less (i.e., the molar ratio of hydrogen available for reacting to olefinic starting material is preferably between 10:1 and 1:1).
  • the hydrogen can be fed either in the pure state or diluted with an inert gas (e.g., nitrogen, helium or argon).
  • the dihydropolyfluoroalkanes of this invention include the dihydropolyfluoropentane represented by the structural formula CF 3 CHFCHFCF 2 CF 3 ; the dihydropolyfluorohexane represented by the structural formula CF 3 CHFCHFCF 2 CF 2 CF 3 ; and the dihydropolyfluoroheptanes represented by the structural formulae CF 3 CF 2 CHFCHFCF 2 CF 2 CF 3 and CF 3 CHFCHFCF 2 CF 2 CF 2 CF 3 .
  • a process is provided in accordance with this invention for preparing a linear dihydropolyfluoroalkane selected from the group consisting of CF 3 CHFCHFCF 2 CF 3 , CF 3 CHFCHFCF 2 CF 2 CF 3 , CF 3 CF 2 CHFCHFCF 2 CF 2 CF 3 , CF 3 CHFCHFCF 2 CF 2 CF 3 , and CF 3 CF 2 CHFCHFCF 2 CF 3 , which comprises the step of reacting an olefinic starting material in the vapor phase with hydrogen over a Group VIII metal catalyst.
  • the catalyst is from the palladium group.
  • Unsupported metal catalysts and supported metal catalysts wherein the metal is palladium, rhodium, or ruthenium are particularly suitable for use in this process.
  • Supports such as carbon or alumina may be employed.
  • Supported palladium catalysts are preferred.
  • the vapor phase reduction can be carried out at temperatures in the range of from 50°C to 250°C; the preferred temperature range is from 100°C to 200°C.
  • the pressure of the hydrogenation may vary widely from less than 1 atmosphere to 20 or more atmospheres.
  • the molar ratio of hydrogen to olefinic starting material for this process is preferably between 0.5:1 and 4:1, and is more preferably between 0.5:1 and 1.5:1.
  • Palladium and rhodium are the preferred metals, with palladium being the most preferred.
  • the metal catalysts may be supported, for example, on carbon or on alumina, with carbon the preferred support.
  • the liquid phase reduction can be carried out at temperatures ranging from 0°C to 200°C, with a preferred range being from 25°C to 100°C.
  • the pressure of the hydrogenation may vary widely from less than 1 atmosphere to 30 atmospheres or more.
  • the molar ratio of hydrogen to olefinic starting material for this process is preferably between 1:1 and 100:1 and is more preferably between 1:1 and 10:1.
  • This hydrogenation is preferably carried out in the absence of a polar solvent.
  • the reduction may be carried out neat (i.e., using no solvent or diluent) or in the presence of a non-polar solvent.
  • Suitable non-polar solvents which may be employed include inert low dielectric alkanes (e.g., nonane and cyclohexane) or low dielectric aromatics (e.g., toluene, benzene and orthoxylene).
  • Hydrogen iodide for the reaction may be provided by several methods.
  • the reaction may be run with stoichiometric HI.
  • the reaction may be run with catalytic amounts of HI in the presence of hydrogen.
  • the reaction may also be run with hydrogen using catalytic amounts of iodine. This latter method is preferred for batch reactions and for ease of handling.
  • This reaction may be accomplished in the absence of supported metal catalysts; and indeed the catalyst for this reaction typically consists essentially of iodine and/or hydrogen iodide.
  • the reaction temperature for this reaction should generally be from 100°C to 500°C.
  • a preferred temperature range is from 200°C to 400°C.
  • This reaction may be run at a pressure of from 3.4 to 340 atm. (50 psi to 5000 psi), with 34 to 102 atm. (500 psi to 1500 psi) being preferred.
  • the amount of hydrogen provided for contact with the olefinic starting material should represent at least one molecule of hydrogen for each olefinic bond to be saturated, and is preferably 10 times said minimum, or less (i.e., the molar ratio of hydrogen available for reacting to olefinic starting material is preferably between 10:1 and 1:1).
  • the hydrogen can be fed either in the pure state or diluted with an inert gas (e.g., nitrogen, helium or argon).
  • the processes of this invention wherein the olefinic starting material is hydrogenated over a palladium group metal catalyst allow for selecting between processes wherein the major product (i.e., above 50 mole percent based upon the amount of olefinic starting material hydrogenated) is a dihydropolyfluoroalkane, and processes wherein the major product is a trihydropolyfluoroalkane.
  • liquid phase processes wherein polar solvents are used favor the production of trihydropolyfluoroalkanes and may thus be used to produce trihydropolyfluoroalkanes as the major product.
  • a liquid phase process using polar solvents may be used to produce about 65 mole percent or more trihydropolyfluoroalkane product.
  • Examples 1, 2, 4, 7, 10 and 15 herein are referenced as examples of trihydrononafluoropentane preparation
  • vapor phase processes, neat liquid phase processes, and liquid phase processes using non-polar solvents favor production of dihydropolyfluoroalkanes and may thus be used to produce dihydropolyfluoroalkanes as the major product of the reaction.
  • a vapor phase process, a neat liquid process, or a liquid phase process using non-polar solvents may be used to produce about 65 mole percent or more dihydropolyfluoroalkane product. Examples 5, 6, 8, 9, 11, 12, 13 and 14 herein are referenced as examples of dihydropolyfluoroalkane preparation.
  • Example 13 and 14 indicate further that the use of an appropriate solvent can result in the formation of one diastereomeric dihydro compound selectively.
  • Example 8 illustrates the high selectivity for introduction of two hydrogens which is possible in a vapor phase reaction using a palladium catalyst.
  • the processes of this invention which do not use metal catalysts and which react olefinic starting material with hydrogen in the presence of iodine and/or hydrogen iodide or with hydrogen iodide, allow for producing as the major product a polyfluoroalkane wherein exactly two hydrogens have been added to said olefinic starting material.
  • the processes using iodine and/or hydrogen iodide may be used to produce about 95 mole percent or more of product wherein exactly two hydrogens have been added to the olefinic starting material.
  • 2,3-dihydrodecafluoropentane of over 99% purity can be obtained by the reaction of one part perfluoropentene-2 with excess hydrogen and about 0.5 part of iodine at 300°C and 68 atm (1000 psi) for 20 hours (see Example 3 herein).
  • the dihydro and trihydro linear polyfluoropentanes, polyfluorohexanes and polyfluoroheptanes of this invention are useful as solvents (especially those compounds having boiling points of 100°C or less). They are replacements for currently environmentally suspect chlorofluorocarbons such as trichlorotrifluoroethane. They have zero ozone depletion potential. They are non-flammable. These polyfluoroalkanes may be used by themselves or in combination with other miscible solvents as cleaning agents or defluxing agents for solid surfaces, for example, printed wire boards.
  • the compounds having boiling points above 75°C are useful as vapor degreasers.
  • the compounds of this invention may also be used as drying agents.
  • compositions suitable for use in cleaning operations can be prepared which comprise a mixture of dihydro- and/or trihydropolyfluoroalkanes of this invention with one or more compounds selected from the group consisting of alcohols, ethers, esters, ketones, nitromethane, acetonitrile, and halogenated hydrocarbons.
  • the preferred alcohols and halogenated hydrocarbons contain from 1 to 4 carbon atoms; the preferred ethers contain from 2 to 6 carbon atoms; and the preferred esters and ketones contain from 3 to 6 carbon atoms.
  • suitable alcohols include methanol, ethanol and isopropanol.
  • suitable ethers include tetrahydrofuran and diethylether.
  • suitable ketones include acetone and methylethylketone.
  • suitable halogenated hydrocarbons include methylene chloride (i.e., dichloromethane), 1,1,2-trichloro-1,2,2-trifluoroethane, dichlorodifluoroethane, trichloroethene, and trans-1,2-dichloroethylene.
  • such compositions contain at least about 5 percent by weight total of the polyfluoroalkanes of this invention; and can contain up to 99 percent by weight, or even more thereof.
  • compositions include mixtures of CF 3 CHFCHFCF 2 CF 3 , CF 3 CH 2 CHFCF 2 CF 3 or CF 3 CHFCH 2 CF 2 CF 3 (especially CF 3 CHFCHFCF 2 CF 3 ) with one or more of said alcohols, ethers, esters, ketones, nitromethane, acetonitrile and halogenated hydrocarbons.
  • Most preferred with respect to ozone depletion potential are compositions in which no component contains chlorine.
  • the mixtures of this invention are useful in a wide variety of processes for cleaning solid surfaces which comprise treating said surface therewith. Applications include removal of flux and flux residues from printed circuit boards contaminated therewith.
  • compositions which comprise an admixture of effective amounts of one or more of the dihydropolyfluoroalkanes and trihydropolyfluoroalkanes of this invention with one or more solvents selected from the group consisting of alcohols, ethers, esters, ketones, nitromethane, acetonitrile and halogenated hydrocarbons to form an azeotrope or azeotrope-like mixture are considered especially useful.
  • solvents selected from the group consisting of alcohols, ethers, esters, ketones, nitromethane, acetonitrile and halogenated hydrocarbons to form an azeotrope or azeotrope-like mixture.
  • azeotropic compositions consisting essentially of 95.3 weight percent CF 3 CHFCHFCF 2 CF 3 and 4.7 weight percent methanol (boiling point 39.9°C); consisting essentially of 97.1 weight percent CF 3 CHFCHFCF 2 CF 3 and 2.9 weight percent ethanol (boiling point 43.4°C); consisting essentially of 97.4 weight percent CF 3 CHFCHFCF 2 CF 3 and 2.6 weight isopropanol (boiling point 45.5°C); consisting essentially of 60.5 weight percent CF 3 CHFCHFCF 2 CF 3 , 36.2 weight percent trans 1,2-dichloroethylene, and 3.3 weight percent methanol (boiling point about 35.3°C); and consisting essentially of 63.9 weight percent CF 3 CHFCHFCF 2 CF 3 , 35.1 weight percent trans 1,2-dichloroethylene and 1.0 weight percent ethanol (boiling point 35.1°C) are considered useful for cleaning printed circuit board contaminated with flux and flux-re
  • compositions of the invention may be used in conventional apparatus, employing conventional operating techniques.
  • the solvent(s) may be used without heat if desired, but the cleaning action of the solvent may be assisted by conventional means (e.g., heating, agitation, etc.).
  • conventional means e.g., heating, agitation, etc.
  • ultrasonic irradiation it may be advantageous to use ultrasonic irradiation in combination with the solvent(s).
  • compositions provided in accordance with this invention can be used in cleaning processes such as is described in U.S. Patent No. 3,881,949 and U.S. Patent No. 4,715,900, both of which are incorporated herein by reference.
  • the mixtures of the instant invention can be prepared by any convenient method including mixing or combining the desired amounts of the components.
  • a preferred method is to weigh the desired amounts of each component and thereafter combine them in an appropriate container.
  • the product mixture of this example was shown (by further exposing it to hydrogen in the presence of a Pd/C catalyst) to be stable to reduction conditions once it is formed, indicating that loss of F - or HF leading to trihydro product occurs while the olefin is reacting on the catalyst surface.
  • a metal rocker tube charged with 97.4 g (0.384 mol) of iodine and 191.8 g (0.767 mol) of perfluoropentene-2 was cooled, evacuated, pressured with 6,8 atm. (100 psi) of hydrogen, and heated to 300°C. Hydrogen pressure was raised to 68 atm. (1000 psi) and maintained there while the vessel was kept at 300°C for 1 day.
  • the vessel was cooled to 5°C, gases were vented, and the cold product (157.2 g, 99% pure by GC) was washed with cold aqueous Na 2 S 2 O 3 , dried over Na 2 SO 4 , to give perfluoro-2H,3H-pentane, bp 43-52°C, as two diastereomers in 49:51 ratio.
  • the distillate was shown by GC and NMR analyses to be composed of 5% of unreacted perfluoropentene-2, 26% of the olefins perfluoro-2H-pentene-2/perfluoro-3H-pentene-2, 64% of perfluoro-2H,2H,3H-pentane and perfluoro-2H,3H,3H-pentane, and 13% of perfluoro-2H,3H-pentane.
  • the ratio of trihydro- to dihydropentanes was 83:17. It is expected that this ratio would be higher if the monohydroolefins were further reduced.
  • the mixture was treated with 4.2 g of NaF and distilled to give 17.6 g of crude product, bp 47-48°C.
  • This reaction provided a preferred polar solvent for very selectively reducing perfluorinated linear internal olefins to trihydro derivatives with hydrogen and metal catalyst under mild conditions.
  • Example 8 was substantially repeated except that the catalyst was 5.0 g of 1% ruthenium on carbon and the operating temperature was 200°C. Under these conditions perfluoropentene-2 conversion was 41.2% and the combined selectivity to the perfluoro-2H,3H-pentane isomers was 70.4%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)

Claims (25)

  1. Verbindung, ausgewählt aus der Gruppe, bestehend aus CF3CHFCHFCF2CF3, CF3CH2CHFCF2CF3, CF3CHFCH2CF2CF3, CF3CH2CH2CF2CF3, CF3CHFCHFCF2CF2CF3, CF3CH2CHFCF2CF2CF3, CF3CHFCH2CF2CF2CF3, CF3CF2CH2CHFCF2CF3, CF3CF2CHFCHFCF2CF2CF3, CF3CHFCHFCF2CF2CF3, CF3CHFCH2CF2CF2CF2CF3, CF3CH2CHFCF2CF2CF2CF3, CF3CF2CHFCH2CF2CF2CF3 und CF3CF2CH2CHFCF2CF2CF3.
  2. Verbindung nach Anspruch 1, die CF3CHFCHFCF2CF3 ist.
  3. Verbindung nach Anspruch 1, die CF3CH2CHFCF2CF3 ist.
  4. Verbindung nach Anspruch 1, die CF3CHFCH2CF2CF3 ist.
  5. Verbindung nach Anspruch 1, die CF3CHFCHFCF2CF2CF3 ist.
  6. Verbindung nach Anspruch 1, die CF3CH2CHFCF2CF2CF3 ist.
  7. Verbindung nach Anspruch 1, die CF3CHFCH2CF2CF2CF3 ist.
  8. Verbindung nach Anspruch 1, die CF3CF2CH2CHFCF2CF3 ist.
  9. Verbindung nach Anspruch 1, die CF3CF2CHFCHFCF2CF2CF3 ist.
  10. Verbindung nach Anspruch 1, die CF3CHFCHFCF2CF2CF2CF3 ist.
  11. Verbindung nach Anspruch 1, die CF3CHFCH2CF2CF2CF2CF3 ist.
  12. Verbindung nach Anspruch 1, die CF3CH2CHFCF2CF2CF2CF3 ist.
  13. Verbindung nach Anspruch 1, die CF3CF2CHFCH2CF2CF2CF3 ist.
  14. Verbindung nach Anspruch 1, die CF3CF2CH2CHFCF2CF2CF3 ist.
  15. Verfahren zur Herstellung eines linearen Trihydropolyfluoralkans, ausgewählt aus der Gruppe, bestehend aus CF3CH2CHFCF2CF3, CF3CHFCH2CF2CF3, CF3CH2CHFCF2CF2CF3, CF3CHFCH2CF2CF2CF3, CF3CF2CH2CHFCF2CF3, CF3CHFCH2CF2CF2CF2CF3, CF3CH2CHFCF2CF2CF2CF3, CF3CF2CHFCH2CF2CF2CF3 und CF3CF2CH2CHFCF2CF2CF3, umfassend die Stufe: Umsetzen eines olefinischen Ausgangsmaterials in der flüssigen Phase mit Wasserstoff über einem Metallkatalysator aus der Palladiumgruppe in Gegenwart eines polaren Lösungsmittels, bei dem das olefinische Ausgangsmaterial dieselbe Anzahl von Kohlenstoffatomen wie das Trihydropolyfluoralkan aufweist und ausgewählt wird aus der Gruppe, bestehend aus CF3CF=CFCF2CF3, CF3CF=CFCF2CF2CF3, CF3CF2CF=CFCF2CF3, CF3CF2CF=CFCF2CF2CF3 und CF3CF=CFCF2CF2CF2CF3, und bei dem das olefinische Ausgangsmaterial seine olefinische Bindung zwischen den Kohlenstoffatomen aufweist, die den Kohlenstoffen entsprechen, die den Wasserstoff in dem Trihydropolyfluoralkan tragen.
  16. Verfahren nach Anspruch 15, bei dem das olefinische Ausgangsmaterial über einem Palladiumkatalysator bei einer Temperatur im Bereich von 0 °C bis 200 °C hydriert wird, bei dem das Molverhältnis von Wasserstoff zu olefinischem Ausgangsmaterial zwischen 1:1 und 100:1 liegt und bei dem das lineare Trihydropolyfluorlalkan das Hauptprodukt der Hydrierung ist.
  17. Verfahren zur Herstellung eines linearen Trihydropolyfluoralkans, ausgewählt aus der Gruppe, bestehend aus CF3CH2CHFCF2CF3, CF3CHFCH2CF2CF3, CF3CH2CHFCF2CF2CF3, CF3CHFCH2CF2CF2CF3, CF3CF2CH2CHFCF2CF3, CF3CHFCH2CF2CF2CF2CF3, CF3CH2CHFCF2CF2CF2CF3, CF3CF2CHFCH2CF2CF2CF3 und CF3CF2CH2CHFCF2CF2CF3, umfassend die Stufe: Umsetzen eines olefinischen Ausgangsmaterials bei einer erhöhten Temperatur mit Wasserstoff in Gegenwart von wenigstens einem Material, das aus der Gruppe ausgewählt wird, die besteht aus Iod, Iodwasserstoff, oder mit Iodwasserstoff, bei dem das olefinische Ausgangsmaterial dieselbe Anzahl von Kohlenstoffatomen wie das Trihydropolyfluoralkan aufweist und ausgewählt wird aus der Gruppe, die besteht aus CF3CH=CFCF2CF3, CF3CF=CHCF2CF3, CF3CH=CFCF2CF2CF3, CF3CF=CHCF2CF2CF3, CF3CF2CH=CFCF2CF3, CF3CF2CH=CFCF2CF2CF3, CF3CF2CF=CHCF2CF2CF3, CF3CH=CFCF2CF2CF2CF3 und CF3CF=CHCF2CF2CF2CF3, und bei dem das olefinische Ausgangsmaterial seine olefinische Bindung zwischen den Kohlenstoffatomen aufweist, die den Kohlenstoffen entsprechen, die den Wasserstoff in dem Trihydropolyfluoralkan tragen.
  18. Verfahren zur Herstellung eines linearen Dihydropolyfluoralkans, ausgewählt aus der Gruppe, bestehend aus CF3CHFCHFCF2CF3, CF3CHFCHFCF2CF2CF3, CF3CF2CHFCHFCF2CF2CF3, CF3CHFCHFCF2CF2CF2CF3 und CF3CF2CHFCHFCF2CF3, umfassend die Stufe: Umsetzen eines olefinischen Ausgangsmaterials mit Wasserstoff in der Dampfphase über einem Metallkatalysator aus der Palladiumgruppe, wobei das olefinische Ausgangsmaterial dieselbe Anzahl von Kohlenstoffatomen wie das Dihydropolyfluoralkan besitzt und ausgewählt wird aus der Gruppe, bestehend aus CF3CF=CFCF2CF3, CF3CF=CFCF2CF2CF3, CF3CF2CF=CFCF2CF3, CF3CF2CF=CFCF2CF2CF3 und CF3CF=CFCF2CF2CF2CF3, und bei dem das olefinische Ausgangsmaterial seine olefinische Bindung zwischen den Kohlenstoffatomen besitzt, die den Kohlenstoffen entsprechen, die den Wasserstoff in dem Dihydropolyfluoralkan tragen.
  19. Verfahren nach Anspruch 18, bei dem das olefinische Ausgangsmaterial über einem Palladium-auf-Aluminiumoxid-Katalysator bei einer Temperatur im Bereich von 50 °C bis 250 °C hydriert wird, bei dem das Molverhältnis von Wasserstoff zu olefinischem Ausgangsmaterial zwischen 0,5:1 und 4:1 liegt und bei dem das lineare Dihydropolyfluoralkan das Hauptprodukt der Hydrierung ist.
  20. Verfahren zur Herstellung eines linearen Dihydropolyfluoralkans, ausgewählt aus der Gruppe, bestehend aus CF3CHFCHFCF2CF3, CF3CHFCHFCF2CF2CF3, CF3CF2CHFCHFCF2CF2CF3, CF3CHFCHFCF2CF2CF2CF3 und CF3CF2CHFCHFCF2CF3, umfassend die Stufe: Hydrierung eines olefinischen Ausgangsmaterials in der flüssigen Phase über einem Metallkatalysator aus der Palladiumgruppe in Abwesenheit eines polaren Lösungsmittel, bei dem das olefinische Ausgangsmaterial dieselbe Anzahl von Kohlenstoffatomen wie das Dihydropolyfluoralkan besitzt und ausgewählt wird aus der Gruppe, bestehend aus CF3CF=CFCF2CF3, CF3CF=CFCF2CF2CF3, CF3CF2CF=CFCF2CF3, CF3CF2CF=CFCF2CF2CF3 und CF3CF=CFCF2CF2CF2CF3, und bei dem das olefinische Ausgangsmaterial seine olefinische Bindung zwischen den Kohlenstoffatomen besitzt, die den Kohlenstoffen entsprechen, die den Wasserstoff in dem Dihydropolyfluoralkan tragen.
  21. Verfahren nach Anspruch 20, bei dem das olefinische Ausgangsmaterial über einem Palladiumkatalysator bei einer Temperatur im Bereich von 0 °C bis 200 °C hydriert wird, bei dem das Molverhältnis von Wasserstoff zu olefinischem Ausgangsmaterial zwischen 1:1 und 100:1 liegt und bei dem das lineare Dihydropolyfluoralkan das Hauptprodukt der Hydrierung ist.
  22. Verfahren zur Herstellung eines linearen Dihydropolyfluoralkans, ausgewählt aus der Gruppe, bestehend aus CF3CHFCHFCF2CF3, CF3CHFCHFCF2CF2CF3, CF3CF2CHFCHFCF2CF2CF3, CF3CHFCHFCF2CF2CF2CF3 und CF3CF2CHFCHFCF2CF3, umfassend die Stufe: Umsetzen eines olefinischen Ausgangsmaterials bei einer erhöhten Temperatur mit Wasserstoff in Gegenwart von wenigstens einem Material, das aus der Gruppe ausgewählt wird, die besteht aus Iod und Iodwasserstoff, oder mit Iodwasserstoff, bei dem das olefinische Ausgangsmaterial dieselbe Anzahl von Kohlenstoffatomen wie das Dihydropolyfluoralkan besitzt und ausgewählt wird aus der Gruppe, bestehend aus CF3CF=CFCF2CF3, CF3CF=CFCF2CF2CF3, CF3CF2CF=CFCF2CF3, CF3CF2CF=CFCF2CF2CF3 und CF3CF=CFCF2CF2CF2CF3, und bei dem das olefinische Ausgangsmaterial seine olefinische Bindung zwischen den Kohlenstoffatomen besitzt, die den Kohlenstoffen entsprechen, die den Wasserstoff in dem Dihydropolyfluoralkan tragen.
  23. Zusammensetzung, die ein Gemisch umfaßt aus einem oder mehreren der Verbindungen nach Anspruch 1 mit einer oder mehreren Verbindungen, ausgewählt aus der Gruppe, bestehend aus Alkoholen, die 1 bis 4 Kohlenstoffatome enthalten, Estern, die 3 bis 6 Kohlenstoffatome enthalten, Ethern, die 2 bis 6 Kohlenstoffatome enthalten, Ketonen, die 3 bis 6 Kohlenstoffatome enthalten, halogenierten Kohlenwasserstoffen, die 1 bis 4 Kohlenstoffatome enthalten, Acetonitril und Nitromethan.
  24. Zusammensetzung nach Anspruch 23, welches ein Gemisch ist aus CF3CHFCHFCF2CF3, CF3CH2CHFCF2CF3 oder CF3CHFCH2CF2CF3 mit einem oder mehreren der Alkohole, Ether, Ester, Ketone, halogenierten Kohlenwasserstoffe, Acetonitril und Nitromethan.
  25. Zusammensetzung nach Anspruch 24, die ein Gemisch mit CF3CHFCHFCF2CF3 ist.
EP91918761A 1990-10-11 1991-10-10 Gesättigte, lineare polyfluorkohlenwasserstoffe, verfahren zu ihrer herstellung und ihre verwendung in reinigungsmitteln Expired - Lifetime EP0552252B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US07/595,840 US5171902A (en) 1990-10-11 1990-10-11 Saturated linear polyfluorohydrocarbons, processes for their production, and their use in cleaning compositions
US595840 1990-10-11
PCT/US1991/007240 WO1992006941A1 (en) 1990-10-11 1991-10-10 Saturated linear polyfluorohydrocarbons, processes for their production, and their use in cleaning compositions

Publications (3)

Publication Number Publication Date
EP0552252A1 EP0552252A1 (de) 1993-07-28
EP0552252A4 EP0552252A4 (en) 1993-09-22
EP0552252B1 true EP0552252B1 (de) 1996-06-19

Family

ID=24384892

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91918761A Expired - Lifetime EP0552252B1 (de) 1990-10-11 1991-10-10 Gesättigte, lineare polyfluorkohlenwasserstoffe, verfahren zu ihrer herstellung und ihre verwendung in reinigungsmitteln

Country Status (14)

Country Link
US (5) US5171902A (de)
EP (1) EP0552252B1 (de)
JP (1) JP3162379B2 (de)
KR (2) KR100242045B1 (de)
CN (2) CN1033320C (de)
AR (1) AR246943A1 (de)
AU (1) AU8764491A (de)
DE (1) DE69120426T2 (de)
ES (1) ES2089238T3 (de)
HK (1) HK207496A (de)
MX (1) MX9101530A (de)
RU (1) RU2073664C1 (de)
WO (1) WO1992006941A1 (de)
ZA (1) ZA918127B (de)

Families Citing this family (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5064560A (en) * 1990-10-11 1991-11-12 E. I. Du Pont De Nemours And Company Ternary azeotropic compositions of 43-10mee (CF3 CHFCHFCH2 CF.sub.
US5064559A (en) * 1990-10-11 1991-11-12 E. I. Du Pont De Nemours And Company Binary azeotropic compositions of (CF3 CHFCHFCF2 CF3) with methanol or ethanol or isopropanol
US5531916A (en) * 1990-10-03 1996-07-02 E. I. Du Pont De Nemours And Company Hydrofluorocarbon cleaning compositions
US5171902A (en) * 1990-10-11 1992-12-15 E. I. Du Pont De Nemours And Company Saturated linear polyfluorohydrocarbons, processes for their production, and their use in cleaning compositions
US5250213A (en) * 1991-05-06 1993-10-05 E. I. Du Pont De Nemours And Company 1,1,1,2,2,3,3,4,4,5,6-undecafluorohexane and use thereof in compositions and processes for cleaning
US5424002A (en) * 1991-08-26 1995-06-13 Daikin Industries, Ltd. Solvent composition comprising mixture of polyfluoroalkane and lower alcohol
US5268122A (en) * 1991-08-28 1993-12-07 E. I. Du Pont De Nemours And Company Gem-dihydropolyfluoroalkanes and monohydropolyfluoroalkenes, processes for their production, and use of gem-dihydropolyfluoroalkanes in cleaning compositions
US6355113B1 (en) 1991-12-02 2002-03-12 3M Innovative Properties Company Multiple solvent cleaning system
WO1993016023A1 (en) * 1992-02-06 1993-08-19 Daikin Industries, Ltd. 1,1,1,2,2,5,5,5-octafluoropentane and production thereof
US5288422A (en) * 1993-03-15 1994-02-22 Alliedsignal Inc. Azeotrope-like compositions of 1,1,1,3,3,5,5,5-octafluoropentane, chlorinated ethylenes, and optionally nitromethane
US5290473A (en) * 1993-03-15 1994-03-01 Alliedsignal Inc. Azeotrope-like compositons of 1,1,1,3,3,5,5,5-octafluoropentane, C1-C5 alkanol and optionally nitromethane
JP3407379B2 (ja) * 1993-06-10 2003-05-19 ダイキン工業株式会社 １，１，１，３，３−ペンタフルオロプロパンの製造方法
US5696307A (en) * 1994-01-21 1997-12-09 Alliedsignal Inc. Hydrofluoroalkanes as cleaning and degreasing solvents
US5545769A (en) * 1994-09-29 1996-08-13 E. I. Du Pont De Nemours And Company Process for the manufacture of selected halogenated hydrocarbons containing fluorine and hydrogen and compositions provided therein
US6242658B1 (en) 1996-03-28 2001-06-05 E. I. Dupont De Nemours And Company Process for the manufacture of fluorine-substituted hydrocarbons
US5811473A (en) * 1996-04-02 1998-09-22 Loctite Corporation Primer activator composition for anaerobic adhesives
AU732754B2 (en) 1996-08-02 2001-04-26 Loctite Corporation Non-ozone depleting co-solvent compositions
US5749956A (en) 1996-08-02 1998-05-12 Loctite Corporation Non-ozone depleting co-solvent compositions and adhesive promoter compositions based thereon
JPH10316597A (ja) * 1997-05-15 1998-12-02 Agency Of Ind Science & Technol 弗素化飽和炭化水素
WO1998051649A1 (fr) * 1997-05-15 1998-11-19 Nippon Zeon Co., Ltd. Hydrocarbures fluores satures, compositions de ces produits, fluide a base de polymere, et procede de fabrication de feuille polymere
DE69840266D1 (de) * 1997-05-16 2009-01-08 Nippon Zeon Co Polymer enthaltende flüssigkeit und verfahren zur herstellung eines polymerfilms
CN1127462C (zh) * 1997-12-26 2003-11-12 日本瑞翁株式会社 含－ch2－chf－基团的化合物的制备方法
FR2781499B1 (fr) 1998-07-24 2000-09-08 Atochem Elf Sa Compositions de nettoyage ou de sechage a base de 1,1,1,2,3,4,4,5,5, 5 - decafluoropentane
WO2004085049A2 (en) * 2003-03-28 2004-10-07 The Regents Of The University Of California Preparation and application of encoded bead aggregates in combinatorial chemistry
KR20060132888A (ko) * 2004-01-30 2006-12-22 그레이트 레이크스 케미칼 코퍼레이션 조성물, 할로겐화 조성물, 화학적 제조 및 텔로머화 방법
US7943567B2 (en) * 2004-01-30 2011-05-17 E.I. Du Pont De Nemours And Company Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers
US20070276167A1 (en) * 2004-01-30 2007-11-29 Stephan Brandstadter Compositions, Halogenated Compositions, Chemical Production, and Telomerization Processes
WO2005074639A2 (en) * 2004-01-30 2005-08-18 Great Lakes Chemical Corporation Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers
US7476331B2 (en) * 2005-02-09 2009-01-13 E I Du Pont Nemours And Company Compositions comprising 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane and uses thereof
US20070027349A1 (en) * 2005-07-28 2007-02-01 Stephan Brandstadter Halogenated Compositions
AU2006275700A1 (en) * 2005-07-28 2007-02-08 Great Lakes Chemical Corporation Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers
WO2007013169A1 (ja) 2005-07-29 2007-02-01 Du Pont-Mitsui Fluorochemicals Co., Ltd. 放射性物質の除染用溶剤組成物及び除染材、並びに放射性物質の除染方法
US7709438B2 (en) * 2005-11-01 2010-05-04 E. I. Du Pont De Nemours And Company Azeotrope compositions comprising nonafluoropentene and hydrogen fluoride and uses thereof
US7385094B2 (en) * 2005-11-01 2008-06-10 E.I. Du Pont De Nemours And Company Azeotrope compositions comprising tridecafluoro-3-heptene and hydrogen fluoride and uses thereof
US7560602B2 (en) * 2005-11-03 2009-07-14 Honeywell International Inc. Process for manufacture of fluorinated olefins
US7902410B2 (en) * 2005-11-03 2011-03-08 Honeywell International Inc. Process for the manufacture of fluorinated alkanes
US8318656B2 (en) 2007-07-03 2012-11-27 E. I. Du Pont De Nemours And Company Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers
EP2179020A1 (de) * 2007-08-23 2010-04-28 E. I. du Pont de Nemours and Company Azeotropische zusammensetzungen mit fluorierten olefinen für reinigungszwecke
RU2461539C2 (ru) * 2007-11-06 2012-09-20 Хонейвелл Интернэшнл Инк. Способ получения фторированных алканов
US8044250B2 (en) * 2007-11-16 2011-10-25 Honeywell International Inc. Manufacture of 1,1,1,2,3,3-hexafluoropropane and 1,1,1,2-tetrafluoropropane via catalytic hydrogenation
WO2010007968A1 (ja) * 2008-07-18 2010-01-21 日本ゼオン株式会社 含水素フルオロオレフィン化合物の製造方法
US8552227B2 (en) * 2009-01-05 2013-10-08 E I Du Pont De Nemours And Company Preparation of hydrofluoroolefins by dehydrofluorination
US8399713B2 (en) * 2009-02-16 2013-03-19 E I Du Pont De Nemours And Company Alkyl perfluoroalkene ethers
US20110028770A1 (en) * 2009-08-03 2011-02-03 Honeywell International Inc. Hydrogenation catalyst
TW201247315A (en) * 2011-05-16 2012-12-01 Du Pont Catalytic hydrogenation of fluoroolefins, alpha-alumina supported palladium compositions and their use as hydrogenation catalysts
RU2504425C1 (ru) * 2012-07-17 2014-01-20 федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Российский государственный университет нефти и газа имени И.М. Губкина" Способ очистки дымовых газов
JP6029400B2 (ja) * 2012-09-21 2016-11-24 Ａｇｃセイミケミカル株式会社 液晶化合物の製造方法
JP6195163B2 (ja) * 2014-02-13 2017-09-13 国立大学法人 千葉大学 ケトンのアルキル化方法
US10233410B2 (en) * 2017-06-15 2019-03-19 Eastman Chemical Company Minimum boiling azeotrope of n-butyl-3-hydroxybutyrate and n-undecane and application of the azeotrope to solvent cleaning
CN112074591B (zh) * 2018-05-03 2022-03-22 科慕埃弗西有限公司 包含全氟庚烯的三元和四元共沸物组合物和类共沸物组合物
JP7229273B2 (ja) * 2018-05-03 2023-02-27 ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー ペルフルオロヘプテンを含む二成分共沸混合物及び共沸混合物様組成物

Family Cites Families (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2550953A (en) * 1944-12-08 1951-05-01 Du Pont Catalytic hydrogenation of unsaturated fluorohydrocarbons
BE534839A (de) * 1954-01-13
GB839756A (en) * 1955-07-01 1960-06-29 Robert Neville Haszeldine Improvements in or relating to the preparation of 1,2,3,4-tetrahydroperfluorobutane and perfluorobutadiene
US2844634A (en) * 1956-04-30 1958-07-22 Collier Carbon & Chemical Co Recovery of nitromethane from nitration mixtures
US2975220A (en) * 1958-11-13 1961-03-14 Pennsalt Chemicals Corp Fluorinated organic compounds
US3042727A (en) * 1959-06-04 1962-07-03 Dow Chemical Co Preparation of fluoroform
US2999815A (en) * 1960-08-11 1961-09-12 Du Pont Azeotropic composition
US2999816A (en) * 1960-08-15 1961-09-12 Du Pont Azeotropic composition
US3573213A (en) * 1968-01-18 1971-03-30 Du Pont Azeotrope of 1,1,2-trichloro-1,2,2-trifluoroethane and nitromethane
GB1330534A (en) * 1970-07-07 1973-09-19 Ici Ltd Solvent compositions
US3728268A (en) * 1970-12-11 1973-04-17 Du Pont Mixtures of 1,1,2-trichloro-1,2,2-trifluoroethane,ethanol and acetone and a ternary azeotrope thereof
US3881949A (en) * 1973-02-27 1975-05-06 Du Pont Vapor degreaser process employing trichlorotrifluoroethane and ethanol
US3903009A (en) * 1973-11-16 1975-09-02 Du Pont Azeotrope of 1,1,2-trichloro-1,2,2-trifluoroethane, ethanol and nitromethane
GB1578933A (en) * 1977-05-24 1980-11-12 Ici Ltd Manufacture of halogenated hydrocarbons
US4418185A (en) 1982-09-20 1983-11-29 The Goodyear Tire & Rubber Company Process for nonaqueous dispersion polymerization of butadiene in the presence of high cis-1,4-polyisoprene as a polymeric dispersing agent
GB8321569D0 (en) * 1983-08-10 1983-09-14 Ici Plc Heat pumps
IT1200806B (it) * 1985-10-21 1989-01-27 Ausimont Spa Procedimento per la preparazione di idroalofluoroalcani
US4715900A (en) * 1987-01-08 1987-12-29 E. I. Du Pont De Nemours And Company Azeotropic compositions of trichlorotrifluoroethane, dichlorodifluoroethane and methanol/ethanol
US4828751A (en) * 1987-08-28 1989-05-09 Pcr, Inc. Solvent composition for cleaning silicon wafers
DE3735467A1 (de) * 1987-10-20 1989-05-03 Bayer Ag Verfahren zur herstellung von fluorierten c(pfeil abwaerts)4(pfeil abwaerts)- bis c(pfeil abwaerts)6(pfeil abwaerts)-kohlenwasserstoffen und neue cyclische fluorierte kohlenwasserstoffe, sowie die verwendung von fluorierten c(pfeil abwaerts)4(pfeil abwaerts)- bis c(pfeil abwaerts)6(pfeil abwaerts)-kohlenwasserstoffen als treibgas und arbeitsfluessigkeit fuer waermepumpensysteme
IT1221776B (it) * 1988-01-15 1990-07-12 Ausimont Spa Processo per la preparazione di 1,2 difluoroetano e di 1,1,2 trifluoroetano
GB9009504D0 (en) * 1990-04-27 1990-06-20 Isc Chemicals Ltd Reduced flammability mixture based on isopropanol
US5097082A (en) * 1990-06-05 1992-03-17 E. I. Du Pont De Nemours And Company Production of saturated halohydrocarbons
US5064560A (en) * 1990-10-11 1991-11-12 E. I. Du Pont De Nemours And Company Ternary azeotropic compositions of 43-10mee (CF3 CHFCHFCH2 CF.sub.
US5100572A (en) * 1990-10-03 1992-03-31 E. I. Du Pont De Nemours And Company Binary azeotropic compositions of polyfluoropentanes and methanol
US5064559A (en) 1990-10-11 1991-11-12 E. I. Du Pont De Nemours And Company Binary azeotropic compositions of (CF3 CHFCHFCF2 CF3) with methanol or ethanol or isopropanol
US5531916A (en) * 1990-10-03 1996-07-02 E. I. Du Pont De Nemours And Company Hydrofluorocarbon cleaning compositions
US5162594A (en) * 1990-10-11 1992-11-10 E. I. Du Pont De Nemours And Company Process for production of polyfluoroolefins
US5171902A (en) * 1990-10-11 1992-12-15 E. I. Du Pont De Nemours And Company Saturated linear polyfluorohydrocarbons, processes for their production, and their use in cleaning compositions
US5250213A (en) * 1991-05-06 1993-10-05 E. I. Du Pont De Nemours And Company 1,1,1,2,2,3,3,4,4,5,6-undecafluorohexane and use thereof in compositions and processes for cleaning
EP0516029B1 (de) 1991-05-28 1995-04-05 Daikin Industries, Limited Verfahren zum Trocknen von Gegenständen

Also Published As

Publication number Publication date
US5504265A (en) 1996-04-02
WO1992006941A1 (en) 1992-04-30
HK207496A (en) 1996-11-29
MX9101530A (es) 1992-06-05
KR100242045B1 (ko) 2000-02-01
JP3162379B2 (ja) 2001-04-25
CN1057331C (zh) 2000-10-11
EP0552252A1 (de) 1993-07-28
AU8764491A (en) 1992-05-20
KR930702260A (ko) 1993-09-08
KR100261402B1 (ko) 2000-07-01
DE69120426D1 (de) 1996-07-25
EP0552252A4 (en) 1993-09-22
RU2073664C1 (ru) 1997-02-20
ES2089238T3 (es) 1996-10-01
CN1060461A (zh) 1992-04-22
CN1033320C (zh) 1996-11-20
AR246943A1 (es) 1994-10-31
DE69120426T2 (de) 1996-12-05
US6506950B1 (en) 2003-01-14
US5683978A (en) 1997-11-04
US5723701A (en) 1998-03-03
US5171902A (en) 1992-12-15
ZA918127B (en) 1993-04-13
CN1139152A (zh) 1997-01-01
JPH05508418A (ja) 1993-11-25

Similar Documents

Publication Publication Date Title
EP0552252B1 (de) Gesättigte, lineare polyfluorkohlenwasserstoffe, verfahren zu ihrer herstellung und ihre verwendung in reinigungsmitteln
US6194619B1 (en) Gem-dihydropolyfluoroalkanes and monohydropolyfluoroalkenes, processes for their production, and use of gem-dihydropolyfluoroalkanes in cleaning compositions
US7335804B2 (en) Direct conversion of HCFC 225ca/cb mixture
US5275669A (en) Method of dissolving contaminants from substrates by using hydrofluorocarbon solvents having a portion which is fluorocarbon and the remaining portion is hydrocarbon
US8536387B2 (en) Process for the synthesis of perfluorobutadiene
US5076956A (en) Compositions of octafluorotrifluoromethylpentane and nonafluorotrifluoromethylpentane and use thereof for cleaning solid surfaces
EP1370624B1 (de) Azeotrop-ähnliche zusammensetzung von 1,1,1,3,3-pentafluorpropan und 1-chlor-1,1,3,3,3-pentafluorpropan
US5545770A (en) Process for manufacture of high purity 1, 1-dichlorotetrafluoroethane
US5696307A (en) Hydrofluoroalkanes as cleaning and degreasing solvents
US5569797A (en) Method of removing olefinic impurities from hydrochlorofluorocarbons
US5250213A (en) 1,1,1,2,2,3,3,4,4,5,6-undecafluorohexane and use thereof in compositions and processes for cleaning
KR20000016199A (ko) 1,1,1,3,3-펜타플루오로프로판의 제조방법_
US5084199A (en) 1,1,2,2,3,3-hexafluorocyclopentane and use thereof in compositions and processes for cleaning
US6143938A (en) Process for perhalocycloalkane purification
US5176757A (en) 1,1,2,2,3,3-hexafluorocyclopentane and use thereof in compositions and processes for cleaning
US6147267A (en) Process for perfluorocycloalkane purification
US5208396A (en) Production of saturated halohydrocarbons
WO1991013846A1 (en) 1,1,2,2,3,3-hexafluorocyclopentane and use thereof in compositions and processes for cleaning
EP0889867B1 (de) Verfahren zur herstellung von mit fluor substituierten kohlenwasserstoffen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19930329

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE ES FR GB IT NL

A4 Supplementary search report drawn up and despatched

Effective date: 19930802

AK Designated contracting states

Kind code of ref document: A4

Designated state(s): DE ES FR GB IT NL

17Q First examination report despatched

Effective date: 19950607

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE ES FR GB IT NL

REG Reference to a national code

Ref country code: ES

Ref legal event code: BA2A

Ref document number: 2089238

Country of ref document: ES

Kind code of ref document: T3

REF Corresponds to:

Ref document number: 69120426

Country of ref document: DE

Date of ref document: 19960725

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2089238

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2089238

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20071004

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20081005

Year of fee payment: 18

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090501

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20100501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100501

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20101020

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20101016

Year of fee payment: 20

Ref country code: GB

Payment date: 20101006

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20101122

Year of fee payment: 20

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20111009

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20111009

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20140826

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20111011